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Prepared by: N. Gonzalez
Metrology Programme for Nanotechnologies in CENAM
(ProMetNano)
Norma Gonzalez, Directorate of Materials Metrology, CENAM
Awareness Seminar: Metrology in Chemistry and Nanometrology
SIM CMWG, San Jose, Costa Rica
May 19, 2016
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Topics
• Issues about measurements
• Overview of nanotechnology in Mexico
• Metrology Programme for Nanotechnologies
• Some activities in nano
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Measurement is the core of modern society
Quality of life
Fair trading
Industrial competitiveness
Workplace health and safety regulations
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World metrology day
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Nanotechnology
Nanotechnology
The application of scientific knowledge to manipulate and control matter in the nanoscale to make use of size- and structure-
dependent properties and phenomena distinct from those associated with individual atoms or molecules or with bulk materials.
(Source: ISO/TS 80004-1:2010)
Nanoscale
Size range from approximately 1 nm to 100 nm (Source: ISO/TS 80004-1:2010)
1814 consumer products from 622 companies in 32 countries
Vance, M. E., Kuiken, T.,
Vejerano, E. P.,
McGinnis, S. P.,
Hochella, M. F., Jr.,
Rejeski, D. and Hull, M.
S.
(2015) Nanotechnology
in the real world:
Redeveloping the
nanomaterial consumer
products
inventory. Beilstein
Journal of
Nanotechnology, 6, 1769-
1780.
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What’s so special about the nanoscale?
Properties of materials are size-dependent in this scale range.
…unique physical, chemical, mechanical, and optical properties of
materials that naturally occur at that scale.
Morphology Size
Silver nano-objects synthetized by A.
Manzano’s group, CINVESTAV Unidad
Queretaro. Image courtesy by FEI Company
Mexico
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Benefits and Risks
The introduction of any new material or product into commerce, there is both the potential for positive societal benefits as well as the potential risk of harm to humans or the environment during the production, use and disposal of these new products.
Due to the unique nature of nanomaterials, the current methodologies employed to conduct risk assessments, toxicological assessments and life cycle analysis of products containing nanomaterials may be ineffective or may not currently exist.
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Characterization and regulatory gaps of nano-products
• No agreed protocols for physico-chemical characterization
• Existing ‘test methods’ may not be suitable for nanoscale devices and dimensions
• Measurement techniques and instruments need to be developed and/or standardized
• Calibration procedures and CRMs needed for measurement instruments at nanoscale
Therefore, on
the basis of the study by
Heinrich et al. [1995] and the
pattern of pulmonary
inflammatory
responses, NIOSH has
determined that exposure to
ultrafine TiO2 should be
considered a potential
occupational carcinogen.
Photothermal therapy of Lewis lung
carcinoma in mice using gold nanoshells on
carboxylated polystyrene spheres
Comex battles Mexican graffiti with nanocoating technology: nano coatings are helping to keep Mexico's infrastructure graffitti-free
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Nanotechnology value chain
Basic scientific research
Applied research
New products
PRE-COMMERCIAL STAGE COMMERCIAL STAGE
Product and process
development
Experimental technological development
Reliable measurements
DISPOSAL
Environmental, health and safety; Regulation, education and ethics
Se tomó como base la ref. González J., Red de Innovación en Nanotecnología en Nuevo León (2014). Cátedra en la Facultad
de Química de la Universidad Autónoma de Querétaro
EDGE OF
KNOWLEDGE
APPLIED
KNOWLEDGE
PRODUCT –
PROCESS
PROTOTYPE
INDUSTRIAL
UPGRADING
COMERCIAL
APPLICATION
MARKET
Nanomaterials Nanointermediates Nano-enable products
Nanotechnology may become
a new non-tariff barrier
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Overview of Nanotechnology in Mexico
Industry
Government
Education and
Research
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Higher education institutions and R+D Resources
58 Institutes
159 Laboratories
17 Pilot plants
4 Networks
Záyago-Lau, E.; Foladori, G., Economía, Sociedad y Territorio, Vol. X, Núm.
32, enero-abril, 2010, pp. 143-178
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Education and Research Capabilities
1. CINVESTAV México
2. CINVESTAV Mérida
3. CINVESTAV Querétaro
4. CINVESTAV Saltillo
5. CIITEC -IPN
6. ESFM -IPN
7. IF- UNAM
8. IQ- UNAM
9. CIE- UNAM
10. IIM-UNAM
11. CFATA-UNAM
12. CCADET- UNAM
13. FC- UNAM
14. CCMC- UNAM
15. IMP
16. ININ
17. CENAM
18. CIMAV
19. CIQA
20. CIDESI
21. CIATEC
22. CICY
23. CICESE
24. CIAD
25. CIATEJ
26. CIBNOR
27. CIDETEQ
28. CIO
29. CIATEQ, A.C.
30. COMIMSA
31. IPICYT
32. BUAP
33. UACH
34. UACJ
35. UANL
36. UASLP
37. UADY
38. UAEH
39. UAM-Azcapotzalco
40. UAM-Iztapalapa
41. UDG
42. UG
43. UNISON
44. UMSNH
45. UV/MICRONA
46. ITC
47. ITS
48. ITH
49. ITQ
50. UDEM
51. UDLA
52. UAMS
53. UTM
54. UPChiapas
55. UAZ
56. ITZ
6-IPN 8 - UNAM
3- Research
Institutions
“Sectorizadas”
14- CPI (PRC),
CONACYT System 25- IES (HEI) 56 Institutions
1
2 3
4
5 6 7
8 9
14
12 13
11
10 15
16
17
18
19
20 21
22
23
24
25
26
27 28 29
30
31
32
33
34
35
36
37 38
39 40
41
42
43
46
45 44
47
48
49
50
51 52 53
54
55
56
34 with more than 10 PhDs
Source: 2008
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4
75
14
28
12
8
1
7
8
1
1
4
2
Innovation Projects related with Nanotechnology
CONACYT Fund for Innovation (2009-2012)
17
1
1
INNOVATION FUND (2009-2011) (COMPANIES)
AREA PERCENTAGE
Nanofillers(polymers 75%) 33%
Nanomedicine/ Nanobiotechnology 16%
Nanostructured coatings 11%
Paper 6%
Others 35%
51 awarded USD 225 000/per project
State Projects Approved
Nuevo León 75 28
Edo. Mex. 28 5
Distrito Federal 17 5
Coahuila 14 5
Guanajuato 12 3
Sonora 8 2
San Luis Potosí 8 2
Querétaro 7 4
Chihuahua 4 1
Jalisco 4 1
Sinaloa 2 0 Baja California
Sur 1 0
Baja California 1 0
Colima 1 0
Hidalgo 1 0
Michoacán 1 0
TOTAL 177 58 Source: Dir. Tec. CONACYT
549 PhD in Mexico 6 % of publications
> 4000/10 years
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Nanoscience and Nanotechnology Network (CONACYT)
1. CIMAV
2. CIQA
3. CIDESI
4. CIATEC
5. CICY
6. CICESE
7. CIAD
8. CIATEJ
9. CIDETEQ
10. CIBNOR
11. CIO
12. CIATEQ, A.C.
13.COMIMSA
14. CINVESTAV México
15. CINVESTAV Querétaro
16. CINVESTAV Saltillo
17. CIITEC del IPN
18. ESFM del IPN
19. IIM de la UNAM
20. IF de la UNAM
21. BUAP
22. UACH
23. UACJ
24. UANL
25.UASLP
26.UADY
27. UAEH
28. UAM-
Azcapotzalco
29. UAM-Iztapalapa
30. UdeG
31. UG
32. UNISON
33. UMSNH
34. UV/MICRONA
35. CENAM
36. IPICYT
37. ITC
38. ITS
39. ITZ
Key Area Leaders Key Competency Areas
Process and equipment design
Nanometrology
Bionanotechnology
Computational Simulation
Polymeric Nanostructures
Inorganic Nanostructures
Nanoparticles
CIDESI
CENAM
CIAD
CINVESTAV
CIQA
CIITEC-IPN
CIMAV
Participation
≈350 Scientists
Source: J. González H., 2010
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n-Industrial Activities
GEOGRAPHIC LOCATION
101 COMPANIES using NANOTECHNOLOGY in 2013
NL
PRODIAT Program for high technology industry
development, nanotechnology,
biotechnology and ICTs
39 %
31 % 10 %
4 % 3 %
2 %
3 %
Foladori et al., 2013
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Nanotechnology Cluster in Nuevo Leon
3 DEVELOPMENT DIRECTIVES
Start Ups
Micro- clustering
20 microcluster with 50 PYMES
Projects with and betwwen
Cluster Companies
Capital
Privado
35 ACTIVE MEMBERS
Source: J. González H., UAQ, 2014
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Nanotech Incubator
Ad
ded
Va
lue
( $
/ k
g )
Re
gis
tred
pa
ten
ts 7
0%
25
% 5
%
Semiconductores
Apparatus Liquid
Crystals
Fiber
Optics
Pharmaceutical
Compositions
Thin
Films
Laser
Beams
Substrates
Semiconducters
Dielectric
Products/Market
High Technology
Products/Market
Medium-high Technology
Products/Market
Medium-Low Technology
Optical
Systems
Nucleic
Acids
Displays
Imaging
Systems
Sources
of Light
Dielectric
Metallic
Óxides
Aqua's
Solutions
Catalysis
Resins
Compositions
Dielectric
Materials
Refractive
Indexes Fibers
Textiles
Water – Air
Purification
Materials
Cement
Materials
Glass
Packaging
Polymers
Steel
Elastomers
Thermoplastics
Food
Products
Personal
Healthcare
Inhibiters
Protease
Water
Treatment
Biotechnology
Scientific/Technological Complexity
Oportunidades para México
Pla
tfo
rms
De
fin
itio
n
for
Na
no
In
cu
ba
tor
in N
L
Value Map of Nanotech Products
Launched / September 2009
CIMAV: Technical Administration
Functions: Start-up and support to existing
companies
Source: J. González H., UAQ, 2014
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Scaled Products from Incubator
UV protection film for agroindustrial use
Bactericide + fungicide Mechanical strength + UV
Low friction coefficient lubricant Hydrophobic and oleophobic properties
v
Nanotech Cluster Members
Mechanical properties improved foam
Source: J. González H., UAQ, 2014
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Stakeholders for standards and regulations
ISO TC 229 Nanotechnology
OECD- Working Party on
Manufactured Nanomaterials
(WPMN)
Consultative Committee for
Amount of Substance – Metrology in
Chemistry
BIPM
VAMAS
National Technical Committee of
Standardization in Nanotechnology and International Standardization
Committee Mirror of ISO TC 229
INDUSTRY EDUCATION AND
RESEARCH GOVERNMENT
Initiative for Nanotechnology development in
Mexico,
Nanoscience and
Nanotechnology Network,
CONACYT
European Commission Projects
Horizon 2020:
BISNANO, NANOSAFETY
United States-Mexico High-Level
Regulatory Cooperation Council
(Nanotechnology)
•Guidelines on regulations for
nanotechnologies to foster
competitiveness and protect the
environment, the human health and the safety of the
consumers
Regulation Bodies:
SE
STPS
COFEPRIS
SAGARPA
SEMARNAT
INECC Competitiveness, strengthening of economy, health and environment
protection
8 published voluntary
Mexican standards
and 8 in preparation
VAMAS TWA-2,
TWA-33, TWA-34
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The National Metrology Institute in Mexico
Staff: 295 people ≈ 155 Technical
activities
4 Technical Areas
731 CMC in
BIPM-KCDB
150 international
comparisons
> 60 on-site peer
reviews
>3000 calibrations/yr
> 300 CRM
> 44 National PT/yr
and other services
Formal activities
since 1994
68 National
Standards
Electrical Physical Materials Mechanical
Electromagnetic measurement
Thermometry
Time and frequency
Radiofrequency
Acoustic and vibrations
Optics and radiometry
Reference materials
Inorganic analysis
Organic analysis
Flow and volume
Force and pressure
Mass and density
Dimensional
Technology
Services
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Mission Support different sectors of society in order to satisfy present and future metrological needs, establishing national measurement standards, developing reference materials and disseminating its accuracy, through technological services of the highest quality, aiming to increase the country’s competitiveness, contribute to sustainable growth and improve the quality of life of citizens.
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The Need for Standards and Metrology
• Nanoscience can only evolve into nanotechnology once the measurement problems and metrology are under control
• Economic impacts from product development and commercialization demand standards
• Workplace safety, environment and health are the key drivers during this transition
• The role of NMIs
• Traceable instrumentation and measurement techniques for calibration
• Development and calibration of artefact standards and reference materials
• Suitable models for uncertainty evaluation
• Conducting international measurement comparisons of independently realized quantities
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Broadening measurement capabilities
SI
m
kg
A
mol s
K
cd
N y N
Size
Metrology Programme
for Nanotechnologies
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ProMetNano Improvement or development of new equipment / measurement devices
Improvement or development of new measurement standards and methods
Support to improve or develop new process
HEI
Industry
Government
Measurements are essential to all stages of materials and product life cycles
Novel measurements capable of probing nanoscale dimensions and nanoscale entities
• Biotechnology
• Climate change
• Energy
• Automotive
• Health
• Safety
• Food
• Aerospace
• Others…
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CENAM Nanometrology – Key areas
Linking the nanometre to the metre
Provide traceability for nanoscale dimensional
measurements using a Metrological Atomic
Force Microscope (m-AFM)
Metrology for nanomaterials
Nanoparticle characterisation
Evaluation of instrumentation
Instrument and method development
Reference materials Narayan Poudyal and J Ping
Liu 2013 J. Phys. D: Appl. Phys.
46 043001
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Traceable dimensional nano measurement
SI m
Iodine-stabilized laser
Calibration of m-AFM interferometry laser
m-AFM
Commercial AFM
Calibration artefacts
Measurement nanoparticles
Unit realization
International agreement
(CGPM /BIPM)
Accredited or final
user’s lab
In-field or lab
calibration
Linking the nanometre to the metre
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Metrology for nanomaterials
Properties cannot be extrapolated from the macro scale.
Enormous variety of nanomaterials and characterization techniques.
Physico‐chemical metrology is still in understanding process.
No consensus about which properties are the crucial ones for both beneficial and detrimental effects.
The interaction of nanomaterials with the environment is crucial but poorly understood.
No routine methods are available for analysing nanomaterials in matrices (metal, ceramics, polymers, …)
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Size measurement
¿What is the right particle diameter?
DLS TEM SEM AFM
8.5 nm ± 0.3 nm 8.9 nm ± 0.1 nm 9.9 nm ± 0.1 nm 13.5 nm ± 0.1 nm
np-Au
Nominal diameter: 10 nm NIST Report of Investigation, RM 8011, 2007
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what is the measurand? which unit?
Identifying and counting particles in air
Identifying and counting their
metabolites in biological matrices
(¿?)
• Measuring their functional properties
(¿?)
But, particles unstable and reactive
• Undergo transformation
Nanoparticle measurements questions
Symmetric objects Morphology
parameters but others…
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Size measurement
• Different physical principles, e.g., • SEM, TEM: electron scattering/diffraction– direct
method • DLS: Brownian motion in a liquid – ‘hydrodynamic’
diameter • AFM: force measurement
• Each type of measurement needs different sample preparation
• Measured ‘size’ is defined differently
• Use of multiple techniques
• Relevance for toxicity testing?
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np-Ag – candidate of reference material
• Why
• One of the most used nanomaterial for manufacturing products,
• One of the most used for research institutions,
• Research and industry labs are interested on it to evaluate electron microscopes and DLS performance and for risk assessment protocols,
• Regulation support,
• Foster synergic collaboration between industry-CENAM-government-HEI.
• Intended uses
• Develop and evaluate in vitro and in vivo assays designed to assess the biological response,
• Evaluate and qualify methodology and instrument performance related to the physical and dimensional characterization of nanoscale particles,
• Facilitate interlaboratory comparisons and benchmarking,
• Develop and evaluate assays to assess the impact of nps in the environment and the risks to human health and safety.
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Nanomaterial candidate
• Mexican company
• Biological process
npAg
TEM 15 nm ± 5.3 nm
DLS 55 nm
UV-VIS
424 nm
Potencial zeta
11.9 mV ± 4.4 mV
APCI-
MS
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Process of RM proposed
Nano-objetos de plata sintetizados por el CINVESTAV-Qro, imagen cortesía de Zeiss
Imagen obtenida por TEM de nanopartículas de plata proporcionadas por Lotto-Labs, cortesía CNMyN-IPN.
Development of
measurement
method and
instrumentation
Method
reproducibility Validation of
method
Test material Reference
material
Certified
reference
material
Production
procedure
Homogeneity
and stability
studies
Certified
assigned value
• What is particle aspect?
– Size
– Morphology
• What is the particle composition?
– Composition of all volume
– Surface composition
– Impurities
• How interact with environment?
– Surface charge
– Aggregation / agglomeration state
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Final thoughts
Metrology at the nanoscale is critical for the development of nanotechnology,
both for scientific understanding and for viable commercial activities.
No single technique will be able to provide all of the critical metrology for
nanoscale systems.
Ongoing challenges include the development of instrumentation with a level of
complexity for use by scientists and in the development of physical
understanding of the response from complex heterogeneous nanometer-scale
systems.
• Useful to consider gateway projects to establish traceability at the nanoscale
• certified reference materials
• instrumentation with embedded traceability
• Many challenges exist
• types of instruments produce different results
• morphology of nanomaterials/nanoparticles influences measurements
• sample preparation is critical
• …
• Cooperation and collaboration between NMIs is the most productive path
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Next steps...
• Consolidate CENAM infrastructure – Laboratories, equipments, human resources.
• Development of Nanometrology Projects in collaboration with RDI institutions, regulatory agencies and industry.
• Strengthening of Standards, Metrology and Conformity Assessment System in Mexico.
• Continue International collaboration.
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Thank you for your attention
Norma González
Centro Nacional de Metrología
MÉXICO
Phone: +52(442) 211 0500
e-mail: [email protected]